JPH072642A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic having beautifying effect, excellent permeability to skin, preventing dark stain and freckle caused by sunburn of skin, effective for retention of beautiful skin, having low irritation to human body, containing a specific phospholipid derivative (salt). CONSTITUTION:A phospholipid derivative of formula I [A is group of formula II (R1 and R2 are 7-21C fatty acid residue) or group of formula III; B is group of formula IV or formula V; M is H, alkali metal or alkaline earth metal] or its salt is mixed with stearic acid, glyceride monostearate, liquid paraffin, propylene glycol, tragacanth gum, an antiseptic, a perfume, purified water, etc., blended under heating, emulsified and cooled to produce a milky lotion. Consequently, the objective cosmetic effective for preventing dark stain and freckle caused by sunburn of skin, effective for retention of beautiful skin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic containing a phospholipid derivative, and more particularly to a cosmetic having a whitening effect and the like and having low irritation to the human body.

[0002]

2. Description of the Related Art With the recent trend toward higher standards of living, cosmetics having safety and functionality for the human body are desired. As such a cosmetic, a whitening cosmetic containing a compound for preventing pigmentation of the skin and maintaining white skin is known. As a substance showing a whitening effect,
Koji acid and arbutin are known, but these are
Since it is water-soluble, its permeability to the skin is poor, and its effect was not sufficient. Further, the water-soluble compound has a drawback that it is poorly mixed with an oily substance and easily separated.

[0003]

Under these circumstances, the present invention has as its object the provision of a whitening cosmetic composition which is excellent in skin penetration and which is well mixed with an oily substance.

[0004]

Means for Solving the Problems As a result of intensive studies by the present inventors on substances having a whitening effect, the phospholipid derivative has an excellent whitening effect, and at the same time, has excellent skin permeability. And completed the present invention. That is, the present invention is a cosmetic containing a phospholipid derivative represented by the general formula (I) or a salt thereof.

[0005]

[Chemical 4]

[Wherein A is

[0007]

[Chemical 5]

(R ₁ and R ₂ are each a carbon number of 7
21 fatty acid residues are shown. ) In the formula, B is

[0009]

[Chemical 6]

In the formula, M represents hydrogen, an alkali metal or an alkaline earth metal. ] A phospholipid derivative represented by the general formula (I) or a salt thereof, an oily substance, water or a polyhydric alcohol, and a surfactant are contained in the cosmetic. The present invention will be described in detail below.

Examples of the phospholipid derivative of the general formula (I) used in the present invention include a phospholipid cordic acid derivative (formula (A)) and a phospholipid arbutin derivative (formula (C)). Further, a lysophospholipid cordieric acid derivative (formula (B)) or a lysophospholipid arbutin derivative (formula (D)) obtained by hydrolyzing these can also be used.

[0012]

[Chemical 7]

[0013]

[Chemical 8]

[0014]

[Chemical 9]

[0015]

[Chemical 10]

Here, R ₁ and R ₂ are each 7 carbon atoms.
~ 21 saturated or unsaturated fatty acid residues are shown. R ₁ and R ₂
May be the same or different. M represents an alkali metal such as Na or K, an alkaline earth metal such as Ca or Mg, or hydrogen. The phospholipid kodjic acid derivative and the phospholipid arbutin derivative are, for example, the method described in JP-A-61-88890 for the phospholipid kodjic acid derivative, and the method described in JP-A-59-187792 for the phospholipid arbutin derivative. Can be manufactured by. That is, a phospholipid and kojic acid or arbutin are produced by using phospholipase D to transfer the phosphatidic acid of phospholipid to the primary alcohol moiety of kojic acid or arbutin.

As the phospholipids used in the reaction, naturally-derived products include, for example, soybean, egg yolk lecithin, animals, plants, microorganisms, synthetic phospholipids, etc., and phospholipids hardened by hydrogenation. Even lipids can be used. As the phospholipase D, any phospholipase D capable of transferring cordieric acid or arbutin to phosphatidic acid can be used.

A specific transfer reaction is as follows. For example, egg yolk lecithin is dissolved in an organic solvent such as ether, to which an aqueous solution of koji acid or arbutin and phospholipase D are added,
It can be performed by mixing and carrying out a transfer reaction. At this time, for example, a sodium salt, a potassium salt, a calcium salt, and a magnesium salt are added to the reaction solution and reacted to obtain a salt of the phospholipid derivative corresponding to the added metal salt. After the reaction, the phospholipid can be recovered from the solution by the method described in the above-mentioned patent publication and purified if necessary to obtain a phospholipid derivative.

The cosmetic of the present invention contains a phospholipid derivative represented by the general formula (I) or a salt thereof, but in addition to this, an oily substance, water or alcohol, and a surfactant are added. It is also possible. The content of the phospholipid derivative or its salt is 0.05 to 20% by weight, preferably 0.
It is 1 to 10% by weight. Examples of the oily substance used in the present invention include oils and fats of animals and plants, waxes, phospholipids, higher alcohols, higher fatty acids, higher aliphatic hydrocarbons, synthetic ester oils, polyhydric alcohols, silicone oils and the like. . Specific examples thereof include fats and oils such as olive oil, soybean oil, castor oil, palm oil, cocoa butter, beef tallow, cod liver oil, butter, and waxes such as
Jojoba oil, beeswax, lanolin, carnauba wax and the like, higher alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol and oleyl alcohol, and higher fatty acids such as lauric acid, palmitic acid, stearic acid, oleic acid and behenin. acid,
Examples of higher aliphatic hydrocarbons such as lanolin fatty acid include liquid paraffin, squalane, vaseline, ceresin, microcrystalline wax and the like, and synthetic ester oils include, for example, butyl stearate, hexyl laurate, diisopropyl adipate, diisopropyl sebacate. Examples of the polyhydric alcohol such as straight chain or branched chain ester such as glycerin, polyglycerin, propylene glycol, polyethylene glycol and the like. The content of these oily substances is preferably 5 to 95% by weight of the whole cosmetic.

Among the surfactants used in the present invention, examples of the anionic surfactant include nonionic surfactants such as alkyl sulfates, fatty acid salts, alkyl phosphates, polyoxyethylene alkyl ether phosphates and sulfates. Examples of the ionic surfactant include glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, and polyglycerin fatty acid ester. For example, alkylbetaine, phosphobetaine, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol and their lyso forms, as well as phosphofatidic acid and its salts, etc. It is. The content of these surfactants is preferably 1 to 10% by weight based on the total weight of the cosmetic.

In addition to the purified water, various additives may be added to the cosmetics of the present invention in a ratio usually used. For example, fragrances, antiseptic germicides, colorants, pigments, antioxidants, thickeners, moisturizers, emulsifiers, emulsion stabilizers, solubilizers, UV absorbers, sequestering agents, medicinal ingredients, etc. are used as product dosage forms. It can be appropriately selected and blended. The cosmetics of the present invention can be applied to any cosmetics such as emulsion, cream, lotion, powder, oil, ointment and the like.

It is known that phospholipids having a glycerol type phosphoric acid ester structure have conventionally been low in irritation to ecology and have characteristics such as surface activity, surface activity and emulsifying property. Therefore, when the phospholipid derivative used in the present invention is also used in cosmetics, it can be expected to have an effect as an emulsifying agent, a dispersant, a gelling agent, a moisturizing agent, and a liposome forming agent, as well as an effect as a whitening agent and an antioxidant. The agent can also be used as a pharmaceutical preparation for external use on the skin.

[0023]

[Examples] Hereinafter, description will be given with reference to production examples of the phospholipid derivative represented by the general formula (I) and compounding examples as cosmetics. However, the present invention is not limited to these examples. Reference Example-1 (Phospholipid chordic acid derivative) 20 g of egg yolk lecithin PC-98N (manufactured by Kewpie Corp.), 100 ml of diethyl ether and 100 ml of distilled water, 4.0 g of NaCl, 20 g of kojic acid, phospholipase D derived from Actinomadura. (Meito Sangyo Co., Ltd.) Add 1,000 units at 30 ℃ for 24 hours
Transferred by the enzyme.

After the reaction, the ether layer was recovered and ether was removed to recover 20 g of the total phospholipid after the transfer reaction. As a result of analyzing this phospholipid by the phospholipid composition analysis method 5.3.3.1-86 of the standard oil and fat analysis test method (edited by Japan Oil Chemistry Association), the following phospholipid kojic acid derivative (formula (A)) newly generated by the transfer reaction was obtained. ) Was included by 50% by weight.

10 g of this phospholipid was redissolved in 50 ml of ether, and 10 ml of phospholipase A ₂ (lecitase 10L: manufactured by Novo Nordisk Bioindustry Co., Ltd.) was added and reacted at 30 ° C. for 24 hours to give β-position fatty acid of phospholipid. Was hydrolyzed. The ether layer was collected and ether was removed to collect 8.2 g of total phospholipid. This phospholipid was used as the standard method for analyzing fats and oils (edited by Japan Oil Chemistry Association), phospholipid composition analysis method 5.3.
As a result of analysis by 3.1-86, the following lysophospholipid kojic acid derivative (formula (B)) newly generated by hydrolysis reaction
Contained 40% by weight. As described in detail in the above-mentioned known method, the transfer reaction of phospholipase D is a reaction in which phosphatidic acid is specifically transferred to the primary hydroxyl group of the acceptor alcohol compound, and the structure of the newly transferred phospholipid kojic acid derivative is Is as in (formula (A)). Phospholipase A ₂ is an enzyme that specifically hydrolyzes β-position glycerin fatty acid ester, and the structure of the newly formed lysophospholipid kojic acid derivative is as shown in (formula (B)).

[0026]

[Chemical 11]

[0027]

[Chemical 12]

Reference Example-2 Egg yolk lecithin PC-98N (manufactured by QP Corporation) 20 g diethyl ether 100 ml and distilled water 100 ml, NaCl 4.0 g, arbutin 100 g, actinomadura-derived phospholipase D (Meito Sangyo Co., Ltd.) 24 hours at 30 ℃ with 2,000 units added
Transferred by the enzyme.

After the reaction, the ether layer was recovered, ether was removed, and 22 g of the total phospholipid after the transfer reaction was recovered. As a result of analyzing this phospholipid by the phospholipid composition analysis method 5.3.3.1-86 of the standard oil and fat analysis test method (edited by Japan Oil Chemistry Association), the following phospholipid arbutin derivative (formula (C)) newly generated by the transfer reaction was obtained. Contained 80% by weight. This phospholipid 10
g was redissolved in 50 ml of ether, and 10 ml of phospholipase A ₂ (lecitase 10L: manufactured by Novo Nordisk Bioindustry Co., Ltd.) was added and reacted at 30 ° C. for 24 hours to hydrolyze β-position fatty acid of phospholipid. The ether layer was collected and ether was removed to collect 8.2 g of total phospholipid. This phospholipid is used as a standard oil and fat analysis test method (edited by Japan Oil Chemistry Association)
As a result of analysis by the phospholipid composition analysis method 5.3.3.1-86 of
64% by weight of the following lysophospholipid arbutin derivative (formula (D)) newly generated by the hydrolysis reaction was contained.

[0030]

[Chemical 13]

[0031]

[Chemical 14]

The four types of transfer reaction phospholipid derivatives obtained in Reference Examples 1 and 2 were purified by the following method, and their infrared absorption was investigated. 0.3 g of the phospholipid sample containing the phospholipid derivative was added to a silica gel-60 (Merck) column (2 x 40
cm), and chloroform: methanol: water = 65: 35:
Elution was carried out with the solvent of 5. TL the elution fraction
Of a single spot newly developed by enzymatic reaction developed on C and (chloroform: methanol: ammonia: water = 50: 20: 2: 1 or chloroform: methanol: acetic acid: water = 170: 25: 25: 3). The phospholipid derivative fractions were collected and collected. IR spectrum was measured by JASCO A202 type infrared spectrophotometer by thin film method, and the result was
Shown in the table.

[0033]

[Table 1] Transfer purified product IR νmax (A) 3300,2950,2860,1740,1640,1460,1380,1230 (B) 3350,2950,2860,1740,1640,1460,1380,1230 (C) 3350, 2920,2850,1740,1500,1465,1380,1220,1175,1100,1070, 1000,880,825,720 (D) 3360,2920,2850,1740,1500,1465,1380,1220,1175,1100,1070, 1000, 880,825,720 Example 1 Table 2 shows an example of raw material blending for liquid cream cosmetics.

[0034]

[Table 2] Phospholipid derivative structure used in combination (A) (B) (C) (D) Raw material% by weight% by weight% by weight% by weight Phospholipid derivatives of Reference Examples 1 and 2 3.8 3.0 1.4 1.2 2. Stearic acid 0.6 0.6 0.6 0.6 3. Glyceride monostearate 1.5 1.5 1.5 1.5 4. Liquid paraffin 10.0 10.0 10.0 10.0 5. Propylene glycol 5.0 5.0 5.0 5.0 6. Tragant gum 1.0 1.0 1.0 1.0 7. Preservative Suitable amount Suitable amount Suitable amount Suitable amount 8. Purified water 78.1 78.9 80.5 80.7 9. Fragrance Appropriate amount Appropriate amount Adequate amount Total 100.0 100.0 100.0 100.0 While the above components 1 to 5 were heated and dissolved and mixed, the components 6 to 9 were separately heated and dissolved, and both were mixed and emulsified at 55 ° C., followed by cooling to prepare an emulsion. As shown in Table 6, the obtained emulsion was found to have skin lightness recovery and whitening effects. As Comparative Example 1,
Instead of the phospholipid derivative of Table 2 in Example 1, the same weight% was used.
Egg yolk lecithin PC-98N (Kewpie Corp.) and 0.3%
Example 1 with the exception of using cordieric acid or arbutin of Example 1.
Manufactured in the same manner as. As shown in Table 6, the cosmetics containing the phospholipid derivative were more excellent in skin lightness recovery and whitening effect as shown in Table 6. Example 2 Table 3 shows an example of blending raw materials for a lotion.

[0035]

Table 3 Phospholipid derivative structure used in combination (A) (B) (C) (D) Raw material% by weight% by weight% by weight% by weight 1. Phospholipid derivatives of Reference Examples 1 and 2 2.5 2.0 0.9 0.8 2. Ethanol 7.5 7.5 7.5 7.5 3. Propylene glycol 5.5 5.5 5.5 5.5 4. Polyoxyethylene hydrogenated castor oil 1.0 1.0 1.0 1.0 5. Glycerin 3.0 3.0 3.0 3.0 6. Tragant gum 0.5 0.5 0.5 0.5 7. Preservative Suitable amount Suitable amount Suitable amount Suitable amount 8. Purified water 80.0 80.5 81.6 81.7 9. Fragrance Appropriate amount Appropriate amount Adequate amount Total 100.0 100.0 100.0 100.0 While the above components 1 to 4 were heated and dissolved and mixed, the components 6 to 9 were separately heated and dissolved, and both were mixed at 55 ° C. and cooled to produce a lotion. As shown in Table 6, the obtained lotion was found to have skin lightness recovery and whitening effects. As Comparative Example 2,
Instead of the phospholipid derivative in Table 3 of Example 2, the same weight% was used.
Egg yolk lecithin PC-98N (Kewpie Corp.) and 0.2%
Example 1 with the exception of using cordieric acid or arbutin of Example 1.
Manufactured in the same manner as. As shown in Table 6, these lotions are
The cosmetics using the phospholipid derivative were clearly superior in skin lightness recovery and whitening effect. Example 3 Example 4 of blending raw materials for cold cream cosmetics
Shown in the table.

[0036]

Table 4 Phospholipid derivative structure used in combination (A) (B) (C) (D) Raw material% by weight% by weight% by weight% by weight Phospholipid derivatives of Reference Examples 1 and 2 5.0 4.0 1.8 1.6 2. Honey honey 10.0 10.0 10.0 10.0 3. Dehydrated lanolin 5.0 5.0 5.0 5.0 4. Liquid paraffin 47.0 47.0 47.0 47.0 5. Polyglycerin fatty acid ester 5.0 5.0 5.0 5.0 6. Borax 1.0 1.0 1.0 1.0 7. Glycerin 5.0 5.0 5.0 5.0 8. Preservative Suitable amount Suitable amount Suitable amount Suitable amount 9. Purified water 22.0 23.0 25.2 25.4 10. Fragrance Suitable amount Suitable amount Suitable amount Total 100.0 100.0 100.0 100.0 While the above ingredients 1 to 6 are heated and dissolved and mixed, 7 to 10 ingredients are separately heated and dissolved, and both are melted and emulsified at 55 ° C to cool the cold cream. Manufactured. As shown in Table 6, the obtained cold cream was found to have skin lightness recovery and whitening effects. As Comparative Example 3, instead of the phospholipid derivative shown in Table 4 in Example 3, the same weight% of yolk lecithin PC-98N was used.
All were manufactured in the same manner as in Example 3 except that (Kewpie Corp.) and 0.4% kojic acid or arbutin were used. As shown in Table 6, in these cold creams, the cosmetics using the phospholipid derivative were obviously superior in skin lightness recovery and whitening effect. Example 4 Example 5 of blending raw materials of anhydrous oily cream cosmetics
Shown in the table.

[0037]

[Table 5] Phospholipid derivative structure used in combination (A) (B) (C) (D) Raw material% by weight% by weight% by weight% by weight Phospholipid derivatives of Reference Examples 1 and 2 5.0 4.0 1.8 1.6 2. Vaseline 25.0 25.0 25.0 25.0 3. Ceresin 15.0 15.0 15.0 15.0 4. Liquid paraffin 25.0 25.0 25.0 25.0 5. Olive oil 24.0 25.0 27.0 27.0 6. Antioxidant 1.0 1.0 1.0 1.0 7. Bentonite 5.0 5.0 5.0 5.0 8. Preservative Suitable amount Suitable amount Suitable amount Suitable amount 9. Dye Suitable amount Suitable amount Suitable amount Suitable amount 10. Fragrance Appropriate amount Appropriate amount Adequate amount Total 100.0 100.0 100.0 100.0 The components 1 to 9 were heated and dissolved and mixed, while 10 were mixed and emulsified at 45 ° C., and cooled to produce an anhydrous oily cream. As shown in Table 6, the obtained oil-free oily cream was found to have skin lightness recovery and whitening effects. Comparative Example 4 was carried out except that the same weight% egg yolk lecithin PC-98N (Kewpie Corp.) and 0.4% kojic acid or arbutin were used instead of the phospholipid derivative in Table 5 of Example 4. Prepared as in Example 4. As shown in Table 6, in these anhydrous oily creams, the cosmetics using the phospholipid derivative were clearly superior in skin lightness recovery and whitening effect. Example 5 A method of performing the skin lightness recovery effect determination method and the whitening effect test method of the cosmetics shown in Examples 1 to 4 will be described. (1) Skin lightness recovery effect determination test method.

UV-B on the upper arm skin of 15 women in their 10s to 30s
The area was irradiated with 2.5 times the minimum erythema dose. The test sample in half irradiation unit after 6 days elapsed since the irradiation is applied, and a non-coated portion of the other half, by measuring the skin reference lightness as a control in each subject, the coating unit skin reference brightness LV ₀ uncoated portion Skin The Munsell value of the brightness was measured by a spectrocolorimeter, and the values were taken as LV _m and LV _m ′, respectively. The skin lightness recovery effect was evaluated according to the following criteria, and the average value of the average evaluation points of 15 persons is shown in Table 6. However, ΔLV = L
V _m -LV _0, which means the _{△ LV '= LV m' -LV} 0 '. Evaluation point Criteria 5 ΔLV-ΔLV ′ ≧ 0.15 4 0.15> ΔLV-ΔLV ′ ≧ 0.1 3 0.10> ΔLV-ΔLV ′ ≧ 0.05 2 0.05> △ LV- △ LV '≧ 0.01 1 0.01> △ LV- △ LV' ≧ 0.00 (2) Whitening, anti-aging effect evaluation test method People who feel that their face has recently become darker, stains , Freckles, 20 women who feel that they have been increasing in number, continue to apply the sample twice daily in the morning and evening, and investigate the effect of whitening improvement after continuous application for 3 months. Is shown in Table 6.

[0039]

[Table 6]

[0040]

The cosmetic of the present invention is excellent as a cosmetic that prevents black spots and freckles due to sunburn of the skin and helps maintain whitening of the skin. Furthermore, the phospholipid derivative of the present invention can be used as a pharmaceutical preparation as a highly safe whitening agent having excellent skin permeability.

Claims (2)

[Claims] 1. A cosmetic comprising a phospholipid derivative represented by the general formula (I) or a salt thereof. [Chemical 1] [Wherein A is (R ₁ and R ₂ each represent a fatty acid residue having 7 to 21 carbon atoms.) In the formula, B is In the formula, M represents hydrogen, an alkali metal or an alkaline earth metal. ] 2. A cosmetic comprising a phospholipid derivative represented by the general formula (I) or a salt thereof, an oily substance, water or a polyhydric alcohol, and a surfactant.